Solvent Extractive Separation of Zirconium and Hafnium from Hydrochloric Acid Solutions by Organophosphorous Extractants and Their Mixtures with Other Types of Extractants

From 1 to 4 M HCl medium, zirconium was selectively extracted over hafnium by organophosphorous extractants (D2EHPA, PC88A, Cyanex 272). In order to increase the separation factor Zr/Hf, mixtures of organophosphorous extractants with amines (Alamine 336, Aliquat 336) or cationic extractants (Versatic acid 10, LIX 63) were employed in 1–4 M HCl medium. Mixtures with Versatic acid 10 and LIX 63 led to depression in the extraction percentages. But the mixture with LIX 63 was found to be the most effective in separating the two metals among the extractant systems tested in this study. The highest separation factor of around 9.5 was obtained with a mixture of 0.01 M LIX 63 + 0.05 M Cyanex 272 at HCl concentration of 2–4 M. The Zr and Hf were effectively stripped from the loaded mixture of LIX 63 + Cyanex 272 by sulfuric acid solution.     

Separation of Cobalt and Zinc from Manganese,Magnesium, and Calcium using a Synergistic Solvent Extraction System Consisting of Versatic 10 and LIX 63

Abstract

The Boleo leach solution contains large amounts of manganese (45 g/L), magnesium (25 g/L) and small amounts of cobalt (0.2 g/L) and zinc (1 g/L) in sea water. Due to the high manganese concentration, it is very difficult to separate cobalt and zinc from manganese, magnesium, and calcium using conventional solvent-extraction processes, which has led to the development of a synergistic solvent extraction (SSX) system consisting of Versatic 10 and LIX®63. By adding 0.4 M LIX 63 to 0.5 M Versatic 10, large synergistic shifts were obtained for cobalt (max. ΔpH₅₀ 4.24) and zinc (max. ΔpH₅₀ 1.62). After a single contact at pH 4.5, the extraction of cobalt was almost complete and that of zinc 80%. The extraction of manganese was 1.55%, and almost no magnesium and calcium were extracted, indicating excellent separation of cobalt and good separation of zinc from manganese, magnesium, and calcium. The SSX system was further optimized to reduce the co-extraction of manganese with the synthetic Boleo demonstration plant solution. It was found that with 0.33 M Versatic 10 and 0.30 M LIX 63, the SSX system composition approached optimum. After a single contact at pH 5.5, the extractions of cobalt and zinc were 93% and 70%, respectively, while the manganese concentration in the loaded organic solution was only 0.28 g/L. The extraction and stripping kinetics of cobalt and zinc were rapid. The SSX system was tested in two integrated pilot-plant trials with excellent results. Baja Mining has planned to implement the SSX circuit in their future Boleo plant.     

Effect of organic extractants on the electrocrystallization of nickel from aqueous sulphate solutions

The effect of the presence of commercial organic extractants LIX 84I, Cyanex 272, D2EHPA, Versatic 10 and TBP with or without Mg²⁺ on various electrodeposition parameters for nickel deposition on stainless steel cathode from aqueous sulphate solutions was investigated. The parameters included cathodic current efficiency, deposit morphology, crystal orientation and cathodic polarization. There was no significant variation in the current efficiency in the presence of these additives, but changes were observed in the deposit morphologies and crystal orientations even though all the deposits were bright, smooth and coherent. Changes were also observed in the cathodic polarization behaviour during nickel electrocrystallization in the presence of these additives. The effect of the additives on the electrokinetic parameter, exchange current density (i ₀) has also been investigated.     

Chemical Reactivity of Tributyl Phosphate with Selected Solvent Extraction Reagents

It has recently been shown that Cyanex 272 can react with tributyl phosphate (TBP) to form the corresponding butyl ester species under both commercial and anhydrous operating conditions. The present work found that acidic organic extractants MEHPA, DEHPA, Ionquest 801, Cyanex 302, Cyanex 301, and decanoic acid also react with TBP to form the corresponding butyl ester species and dibutyl phosphate under anhydrous conditions at 65°C, whereas non-acidic reagents Alamine 308, LIX 84, LIX 63, and Acorga M5640 do not. Excluding MEHPA, the rate of ester formation appears inversely correlated with the pKa of the organic acid used.     

Reagent Degradation in the Synergistic Solvent Extraction System LIX®63/Versatic™10/Nonyl-4PC

Direct solvent extraction of nickel and cobalt from nitrate-based leach liquors has become of interest due to the successful piloting of nitric acid processes for treating nickel laterite ores. The current study investigated the stability of both hydroxyoxime and nonyl-4PC (nonyl-4-pyridine carboxylate) in LIX 63/Versatic 10/nonyl-4PC under conditions relevant to the recovery of nickel and cobalt from a nitrate-based leach liquor with stripping into sulfuric acid. Nonyl-4PC increased both the rate of hydroxyoxime degradation under the pH 1.5 extract conditions required for a potential nickel–cobalt separation process and the rate of cobalt poisoning of LIX 63. Under strip conditions and the pH 4 extract conditions required for co-extraction of nickel and cobalt, nonyl-4PC did not otherwise affect the rate of hydroxyoxime loss. Additionally, the presence of nitrate anions did not increase the loss of either hydroxyoxime or nonyl-4PC. The combination LIX 63/Versatic 10/nonyl-4PC therefore appears prospective for the co-extraction of nickel and cobalt at pH 4 from nitrate-based leach liquors.     

Synthesis,Characterization, and Applications of a New Chelating Resin Containing 4-2-(Thiazolylazo) Resorcinol (TAR)

A new phenol–formaldehyde based chelating resin containing 4-(2-thiazolylazo) resorcinol (TAR) functional groups has been synthesized and characterized by Fourier transform infrared spectroscopy and elemental analysis. Its adsorption behavior for Cu(II), Pb(II), Ni(II), Co(II), Cd(II), and Mn(II) has been investigated by batch and column experiments. The chelating resin is highly selective for Cu(II) in the pH range 2 ～ 3, whereas alkali metal and alkaline earth metal ions such as Na(I), Mg(II), and Ca(II) are not adsorbed even at pH 6. Quantitative recovery of most metal ions studied in this work except Co(II) is achieved by elution with 2M HNO₃ at a flow rate of 0.2 mL min^?1. A similar trend is observed for distribution coefficient values. The quantitative separations achieved on a mini-column of chelating resin include Cd(II) – Cu(II), Mn(II) – Pb(II), Co(II) – Cu(II), Mn(II) – Ni(II), and Mn(II) – Co(II) – Cu(II). The recovery of copper(II) is quantitative (98.0–99.0%) from test solutions (10–50 mg/L) by 1 mol/L HNO₃-0.01 mol/L EDTA. The chelating resin is stable in acidic solutions below 2.5 M HNO₃ or HCl as well as in alkaline solution below pH 11. The adsorption behavior of the resin towards Cu(II) was found to follow Langmuir isotherm and second order rate.     

Synergistic Effect of D2EHPA and Cyanex 272 on Separation of Zinc and Manganese by Solvent Extraction

The effect of bis-2-ethylhexylphosphoric acid (D2EHPA), bis (2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272), and tri-butyl phosphate (TBP) and their mixtures in various proportions for the separation and extraction of zinc and manganese from sulfate solutions were investigated. Experiments were carried out in the pH range of 0.5–5.0 at 25, 40, and 60°C. It was shown that the extraction of zinc and manganese by D2EHPA and/or Cyanex 272 can be increased by the increase in pH and temperature. The synergistic extraction and separation of zinc and manganese with a mixture of D2EHPA and Cyanex 272 was studied and the results showed that mixing the two extractants improved the extraction capacity of the mixture. Increasing the D2EHPA to Cyanex 272 ratio in the organic phase, caused a right shifting of extraction isotherms of manganese and zinc; shifting the manganese curve was more than zinc. The manganese curve had considerable right shifting with 5% D2EHPA and 15% Cyanex 272. TBP did not affect the zinc (Zn) and manganese (Mn) extraction. The stoichiometric coefficients of Zn and Mn were determined with 20% and 5% D2EHPA and 15% Cyanex 272 by applying the slope analysis method. The organic phase was stripped by sulfuric acid.     

Distribution and nature of organic/mineral bound elements in Assam coals, India

This study focuses on the determination and concentration of twelve elements (Na, K, Ca, Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn and Cd) occurring in sub-bituminous Assam coals and their geochemical association. Distribution of these elements between organic and mineral matters was studied. Comparison of the results of three coals has shown that three elements (Mg, Ca and Mn) are significantly organic bound, while five elements (Fe, Co, Ni, Cu and Zn) are significantly mineral bound; Cd is 50% bound to either organic or mineral matter. FTIR and XRD studies reveal qualitative information about the bonding pattern and nature of components of the mineral matters. The results obtained in this study have considerable geochemical and technological interests.     

Selective removal of magnesium from lithium-rich brine for lithium purification by synergic solvent extraction using β-diketones and Cyanex 923

In the production of battery-grade and high-purity Li₂CO₃, it is essential to remove magnesium impurities. The state-of-the-art solvent extraction (SX) process using Versatic Acid 10 and D2EHPA co-extracts 3.3–5.5% lithium, while removing 86–98% magnesium. Here, we demonstrate that synergic SX systems containing a β-diketone (HPMBP, HTTA or HDBM) and Cyanex 923 are highly selective for magnesium extraction over lithium (separation factor α > 1,000). The extracted magnesium and lithium complexes have the stoichiometry of [Mg∙A₂∙(C923)₂] and [Li∙A _x∙(C923)₂] (x = 1, 2), respectively (A represents deprotonated β-diketone). The three β-diketone synergic SX systems all considerably outperformed the Versatic Acid 10 system for magnesium removal from a synthetic solution containing 24 g L⁻¹ Li and 0.24 g L⁻¹ Mg. In a three-stage batch counter-current extraction, the HPMBP and Cyanex 923 synergic SX system removed 100% magnesium with only 0.6% co-extraction of lithium. This excellent Mg/Li separation is the best result reported so far.     

Recovery and Concentration of Metal Ions. II Multimembrane Hybrid System

Abstract

The multimembrane hybrid system (MHS) has been developed and used for the transportation and separation of divalent metal ions from multicomponent solutions. The system consists of three membranes in series

ion-exchange membrane | liquid membrane | ion-exchange membrane

The experiments were performed with liquid membranes composed of di(2-ethylhexyl)phosphoric acid in kerosene and Nafion-120 perfluorosulfonic acid polymer membranes. The fluxes and separation characteristics have been determined for MHS separating a solution of Zn(II), Mn(II), Cu(II), and Ni(II) sulfates as the feed phase, and the strip phase containing sulfuric acid. The results of competitive permeation experiments have shown the selectivity order Zn(II) > Mn(II) > Cu(II) ? Co(II), Ni(II). High separation coefficients were found for Zn(II), Cu(II), and Mn(II) compared to Ni(II) and Co(II).     

ION-EXCHANGE PROPERTIES OF HYDROUS TITANIUM DIOXIDE WITH A FIBROUS FORM OBTAINED FROM POTASSIUM DITITANATE

ABSTRACT

Ion-exchange properties of a new type of hydrous titanium dioxide with a fibrous form, which was obtained from potassium dititanate (K₂O(TiO₂)2), have been studied. The pH titration curve snowed that this material behaved as a bifunctional ion-exchanger. Distribution coefficients of some divalent metal ions on this material were measured as a function of pH and the selectivity series were found to be Ba > Sr > Ca > Mg for alkaline earth metal ions and Cu > Zn > Mn > Co > Ni for divalent transition metal ions. Large separation factors were obtained between some metal ion pairs and the mutual separations such as Cu from Sr, Ca, Mg, Co and Ni, and Mg from Ba and Zn have been achieved on columns of this material.     

Reverse Osmosis Separation of Metal Ions in Acid Mine-Water

Abstract

Cellulose acetate membranes obtained from Osmonics Inc. were characterized in terms of pure water permeability constant, solute transport parameter, and mass transfer coefficient with the reference system of aqueous sodium chloride solution. Reverse osmosis separation behavior of Ca, Mg, Zn, Mn, Cu, Al, and Fe as nitrate, chloride, and sulfate salts was studied. The effect of the addition of sodium sulfate to Mg(ClO₄)₂ and Mn(NO₃)₂ solutions on solute separation was also investigated. Acid mine-water obtained from New Brunswick was subjected to reverse osmosis, and separation of metal ions in the range of 95 to 99 % was obtained along with the recovery of product water of suitable quality for use in recycle operations.     

The effects of chloride ion and organic extradants on electrowon zinc deposits

The effects of chloride ion and the organic extractants: Kelex 100, Versatic 911, di-2-ethylhexyl phosphoric acid, tri-n-butyl phosphate, LIX65N and Alamine 336 on the structure of 1h zinc deposits electrowon from synthetic and industrial acid sulphate electrolytes are presented. Under simulated tankhouse conditions the effect of chloride ion concentration on the zinc deposit morphology and orientation becomes significant only at the 500 mgl^–1 level. The tolerance limit of the zinc deposits to organic extractants such as Kelex 100 is extremely low. In some cases the adverse effect of these organic impurities is offset by the presence of chloride ion in the electrolyte. Purification of electrolyte contaminated with organic extractants by activated charcoal results in a vastly improved zinc deposit structure. Organic extractants such as Kelex 100 and TBP which have an adverse effect on the zinc deposits, also have a pronounced effect on the zinc deposition polarization curve.     

Heavy metal–Soluble starch xanthate interactions in aqueous environments

The effectiveness of the water‐soluble starch xanthate (SSX) process for removal of heavy metals [Hg(II), Cu(II), Cd(II) and Ni(II)] has been evaluated. Removal of Hg(II) and Cu(II) is effective; Cd(II) and Ni(II), less so. The metal [Hg(II)/Cu(II)] binding capacity remains the same in the pH range 3–7. An optimum metal/SSX ratio is observed for maximum metal removal. The metal removal efficiency of SSX appears to be dependent on a specific chemical interaction between metal and SSX and on separation of the metal–xanthate complex from the aqueous phase. An analogy between the metal–SSX system and the colloid–cationic polyelectrolyte system (coagulation and flocculation in water treatment) is observed. The role of ionic strength for metal–SSX system appears to be analogous to the role of indifferent electrolyte in coagulation and flocculation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1325–1332, 1999     

Solvent extraction of nickel from acidic solutions using synergistic mixtures containing pyridinecarboxylate esters. Part 3. Systems based on arylsulphonic acids

The solvent extraction of nickel and calcium from acidic solutions by mixtures of dinonylnaphthalene sulphonic acid (DNNSA) and different pyridinecarboxylate esters (2-, 3- and 4-C₅H₄.CO.OR, where R = n-octyl, 2-ethylhexyl and 2-octyl) in xylene was investigated. In contrast to extraction systems employing DNNSA alone, these mixtures permit the separation of nickel and calcium to be carried out, especially when an excess of the ester is used. The extractability of base metals from sulphate solutions by mixtures of DNNSA (0·25 M ) and isodecyl 3-pyridinecarboxylate (0·25 M ) in Shellsol K decreases through the series Cu > Ni > Al > Co > Ca > Zn > Fe(III) > Mg. Mixtures containing the 2- or 4-ester showed a slightly different selectivity series: Cu > Ni > Co > Zn > Al > Fe(III) ≥ Ca > Mg. In a batch countercurrent experiment, a simulated leach liquor containing Ni 2·15, Mg 5·05 and Ca 0·42 g dm⁻³ (initial pH 3·0) was extracted with the mixed reagent (0·25 M DNNSA plus 0·25 M 4-ester) in four stages at unit phase ratio, without any pH adjustment. The recovery of nickel was 91%, with co-extractions of calcium and magnesium of 14 and 8%, respectively. When the concentration of the 4-ester was increased to 0·50 M , the recovery of nickel increased to 95%, whilst the co-extractions of calcium and magnesium decreased to 4 and 3%, respectively. © 1998 SCI.     

Combustion Synthesis of Metal Chromite Powders

Fine-particle metal chromites (MCr₂O₄, where M = Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn) have been prepared by the combustion of aqueous solutions containing the respective metal nitrate, chromium(III) nitrate, and urea in stoichiometric amounts. The mixtures, when rapidly heated to 350°C, ignite and yield voluminous chromites with surface areas ranging from 5 to 25 m²/g. MgCr₂O₄, sintered in air at 1500°C for 5 h, has a density of 4.0 g/cm³.     

Opposite selectivities of tri-n-butyl phosphate and Cyanex 923 in solvent extraction of lithium and magnesium

The synergic solvent extraction system of tri-n-butyl phosphate (TBP) and FeCl₃ (or ionic liquids, ILs) has been extensively studied for selective extraction of Li from Mg-containing brines. However, Cyanex 923 (C923), which extracts many metals stronger than TBP, has not yet been examined for Li/Mg separation. Here, we report on the unexpected observation that the C923/FeCl₃ system has opposite Li/Mg selectivity compared to the TBP/FeCl₃ system. Detailed investigations show that the opposite selectivity of the C923/FeCl₃ (or IL) system is due to three factors: (1) the strong extraction of Fe by C923 leads to a low concentration of [FeCl₄]⁻ in the system, which is essential for Li extraction; (2) C923 in combination with an IL extracts Mg strongly by an ion-pair mechanism; (3) most importantly, C923 extracts Mg by solvation, resulting in an insufficient concentration of C923 for Li extraction. The unexpected poor Li/Mg selectivity of C923 highlights the irreplaceable role of TBP in the selective recovery of Li.     

Synergistic effects in the solvent extraction of some divalent metals by mixtures of versatic 10 acid and pyridinecarboxylate esters

Pyridinecarboxylate esters were found to cause appreciable synergistic shifts in the pH₅₀ values for the extraction of some divalent base metals by solutions of Versatic 10 acid in xylene. For n-octyl 3-pyridinecarboxylate, the synergistic shifts decreased in the order Ni > Co > Cd > Cu ≈ Fe > Mn > Zn, and for the commercial extractant Acorga DS5443A in the order Ni > Cu > Co > Fe > Cd > Mn > Zn. No synergistic effects were observed for divalent lead, calcium and magnesium. On the basis of the pH₅₀ values obtained, several possible practical metal separations are suggested. No loss of metal-loading capacity was found when the organic phases were contacted with 1 M sulphuric acid for prolonged periods at 30°C. The effect of changes in the structure of a series of isomeric octyl pyridinecarboxylates is reported for one of the smaller cations studied (copper), as well as for one of the larger cations (cadmium).     

Separation of Metals from Sulfated Deep-Sea Ferromanganese Nodules by Adsorbing Colloid Flotation

Abstract

Adsorbing colloid flotation (ACF) is applied to aqueous leach solutions of sulfated deep-sea ferromanganese nodules and their process tailings. Metal cations of Cu, Co, Ni, Mn, Al, and Zn are separated simultaneously by flotation with hydroxide collectors and cationic surfactants from the leach liquors of sulfated ferromanganese nodules. Applications of ACF to the nodule tailings also makes possible the recovery of residual Cu, Co, Ni, Ti, Zn, Al, Fe, Mn, and the separation of Pb and V, the most abundant toxic species in the nodules and tailings.     

The uptake and distribution of mineral nutrients in the banana in response to supply of K,Mg and Mn

The effects of differential K, Mg and Mn supply on the uptake and distribution of N, P, K, Ca, Mg, Na, Mn, Cu and Zn in the Williams banana were examined over the three crop cycles. Plants were grown in sand culture in 1 m³ drainage lysimeters.In terms of total plant uptake the standard solutions used were balanced in respect of P, K and Ca, possibly low in Mg and high in Mn, Cu and Zn compared with field grown plants. K and Mg supply influenced total plant uptake of most elements similar to the way they influenced dry matter production. Exception were total plant uptake of Mg and Cu. High Mn supply depressed the uptake of Mg and Cu and increased the uptake of Mn sevenfold.Increase in K supply reduced the proportion of all nutrients, except K, retained in the roots and increased the proportion located in the fruit. A large proportion (20–36%) of N, P and K were located in the fruit, Ca, Mg and Mn accumulated in the trash (29–44%) and roots were high in Na, Cu and Zn (29–50%).